Thiocarbamic acid derivatives of alkylenebis



Patented July 17, 1951 UNITED STATES- PATENT OFFICE THIOCARBAIVIIG ACID DERIVATIVES OF ALKYLENEBIS (CY OLOHEXYL AMINE) William Kirk, Jr.,' New Castle, Del., assi'gnor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application-March so, 1948, Serial No. 18,070

7 These objects are accomplished by the'inven- 15 tion of dithiocarbamic acids of the formula wherein A is -H or JLSH and n is an integer from 1 to 5, and the salts, esters, and sulfides of said acids. The salts include compounds wherein the H in the CSSH group or groups is replaced by metals or, salt- !orming elements or radicals such as, for example, ammonium or alkyl- .or aryl-substituted ammonium; the esters include compoundswherein the Hin the CSSH group or groups is replaced by alkyl or aryl radicals; and the sulfides include compounds wherein the H in the CSSH group or groups is replaced by wherein p is an integer from 1 to 2 and X and Y are alkyl radicals or may be joined in an alicyclic 1 Claims. (cram-4 29) 2 each, through not more than four methylene groups, 1. e., dialicyclic diamines of the formum where m is a cardinal number not greater than 4, i. e., dialicyclic diamines of the following formula:

wherein n is an integer from 1 to 5, such as, for example, bis(4-aminocyclohexyl), l,2-bis(4-amlnocyclohexyl) ethane, and 1,4-bis(4-aminocyclohexyDbutane. When carbon disulflde is reacted alone with the dialicyclic diamine, the reaction is described by the following equation, regardless of whether an excess of carbon disulfide is prescut or not:

30 wherein n is an integer from 1 to 5. Although the structure of the product of this reaction has been written as a monodithiocarbamic acid of a dialicyclic diamine, it may exist as the salt oi. the acid with the unreacted amino group of the dialicyclic diamine. Further, this salt may be polymeric. I

However, when carbon disulflde in amount sufficient to combine with both of the amino groups of the dialicyclic diamine is reacted with the dialicyclic diamine in the presence of an equivalent amount of a base stronger than the dialicyclic diamine, such as sodium hydroxide, the reaction is described by the following equation:

Gil-NH: ms, zmon 1 tin 'l hese new dithiocarbamic acids and their salts C Hr-CHi CHr-CH! HaNC CH-(CHzh-x-C CHr-C CHPO s NaSlL-NH c are readily prepared by reacting carbon disulfide with dialicyclic diamines having two aminocyclohexyl radicals joined, at the 4 positions of our-0H, s cncm).-10 oHNHyJ-sm 211.0

Other derivatives of the dithiocarbamic acids of this invention can be prepared by the methods, as described later, which methods result in the CHr-C H:

EXAMPLE I Preparation of 4-(4-aminocyclohexylmethyl) cyclohexanedithiocarbamic acid A solution of 10.5 parts of bis(4-aminocyclohexyDmethane (B. P. 112 C./0.5 mm., 132.5 C./1.1 mm., whose preparation is described in copending application Serial No. 615,912, filed September 12, 1945, by Kirk, Schreiber, and Whitman, now abandoned, and application Serial No. 704,796, filed October 21, 1946, by Barkdoll and Whitman) in 35 parts of dry ether was gradually added with stirring to a solution of 12.5 parts of carbon disulfide and 35 parts of dry ether in a glass reactor fitted with a reflux water condenser. A white, crystalline salt separated immediately which was filtered from the reaction mixture and subsequently air-dried. There was obtained 14 parts (98% of theory) of 4-(4-aminocyclohexylmethyl)cyclohexanedithiocarbamic acid. This compound is insoluble in water and ethyl and butyl alcohols. Although this compound has been indicated to be the free dithiocarbamic acid. it may exist as the dithiocarbamic acid salt of the unreacted amino group of the dialicyclic diamine and, further, this salt may be polymeric.

EXAMPLE II Preparation of d sodium 4,4'-methylenebis(cyclohexanedithiocarbamate) A solution of 95 parts of bis(4-aminocyclohexyl) methane in 55 parts of 1,4-dioxane was gradually added with stirring to a mixture of 36 parts of sodium hydroxide, 68.75 parts of carbon disulfide, and 250 parts of water in a reactor fitted with a reflux water condenser. A white precipitate appeared at once. The reaction mixture was warmed on a steam bath for 0.5 hour after the addition wascompleted. The mixture was then cooled to 25 C., diluted with acetone, filtered, and the filter cake washed with acetone and dried in a vacuum oven at 45 C. for 18 hours. There was obtained 105.5 parts (57% of theory) of disodium 4,4'-methylenebis (cyclohexanedithiocarbamate).

EXAMPLE III Preparation of zinc 4,4'-methylenebis(cyclohexanedithiocarbamate) Fifteen and two-tenths (15.2) parts of disodium 4,4 methylenebis(cyclohexanedithiocarbamate) was dissolved in a mixture of 300 parts of water and 270 parts of acetone and the resulting solution filtered. To this solution in an open vessel there was addeda solution of 5.5 parts of anhydrous zinc chloride dissolved in 50 parts of water. The finely divided white precipitate which formed immediately was digested on a steam bath for 30 minutes and then separated from the solution by filtration. There was obtained, after drying to constant weight in a vacuum desiccator at 25 0., 11.5 parts (60.5% of theory) of zinc 4,4- methylenebis(cyclohexanedithiocarbamate) 4 EXAMPLEIV Preparation of copper- 4,4'-methylenebis- (cycloheranedithiocarbamate) A filtered solution of 10 parts of disodium 4,4- methylenebis(cyclohexanedithiocarbamate) in 200 parts of methanol and 150 parts of water was added with stirring to a solution of 12 parts of anhydrous copper sulfate and 100 parts of water in an open glass vessel. A flocculant precipitate formed at once which, after standing overnight in the reaction mixture, was removed by filtration. slurried with water three times, and finally refiltered. There was obtained, after drying in a vacuum oven at 60 C. for 18 hours, 7.95 parts (64% of theory) of copper 4,4'-methylenebis- (cyclohexanedithiocai'bamate) EXAMPLE V Preparation of nickel 4,4'-methylenebis- (cyclohezranedithiocarbamate) A filtered solution of 10 parts of disodium 4,4- methylenebis(cyclohexanedithiocarbamate) in 80 parts of methanol was diluted with parts of water and the resulting solution added with stirring to a solution of 21.5 parts of nickel nitrate hexahydrate and 200 parts of water in an open vessel. A thick precipitate separated at once. The reaction mixture was diluted with 200 parts of water, filtered, and the filter cake washed well with water. There was obtained, after drying at 60 C. in a vacuum oven for 18 hours, 8.3 parts (67.5% of theory) of nickel 4,4'-methylenebis- (cyclohexanedithiocarbamate) Analysis-Calculated for C15H24N2S4Ni: C. 43.0%; H, 5.7%. Found: C, 44.1%; H, 6.3%.

The examples above illustrate the invention utilizing one diamine, namely bis(4-aminocyclohexyl) methane as the source of the dithiocarbamic acid However, the invention is generic to the monoand bis-dithiocarbamic acids, their salts, esters, and sulfides, of alicyclic diamines having two amino cyclohexyl,

CH -CH1 CH- CHrGr radicals joined, at the 4 positions, through a chain of 0 to 4, i. e., not more than 4, methylene groups, i. e., through (cH2)mwhere m is a cardinal number not greater than 4, including the monoand bis-dithiocarbamic acids 01' bis(4-aminocyclohexyl) [Balas and Sevcenko, Collection Czecncsiov. Chem. Communications 3, 171-176 1 9 3 1 l; 1,4 bis(4-aminocyclohexyl) butane, [Ferber, Ber. 62B, 192 (1929)] and bis(4-aminocyclohexyDmethane, 1,2 bis(4-aminocyclohexyDethane and 1,3-bis(4-aminocyclohexyl) propane as disclosed and claimed in the copending application of Kirk, Schreiber and Whitman, Serial No. 615,912, filed September 12, 1945.-

A representative group of salts is listed above. Numerous other salts of the dithiocarbamic acids of this invention from dialicyclic diamines can be prepared in a similar manner. For example, the 4,4-methylenebis(cyclohexanedithiocarbamate) salts of any metallic element may be prepared. Such salts may be prepared by the direct metathesis between a solution of a salt of the metallic element whose dithiocarbamic acid salt is desired with a solution of the readily prepared and more soluble alkali metal salts of the dialicyclic dithiocarbamic acids of this invention. Such metathetical reactions are represented by the following equation, utilizing as examples diylethylenediamine, p-phenylenediamine; cyclic sodium 4,4-methylenebis(cyclohexanedithiocaramines, e. g., piperidine, piperazine, 2.5-dimethylbamate) and cadmium chloride: v piperazine, morpholine; heterocyclic amines, e. g.,

S CHI-Cg: GH -CH; S NaSi JNHC CH-CHr-Cfi CHNH BN6 CdCl,

GH -C CH C 1 CHI-CH. CHI-CH s s %SENHC cnom-c cimn s zmol CHa-C a CHr-C 3 Among such salts, the more important are the alpha aminothiophene, 2 aminopyridine, 2-

salts of univalent and bivalent elements, such amino -4-methylthiazole; tertiary aliphatic as, for example, potassium, lithium, chromium, amines, e. g., trimethylamine, triethylamine; terbarlum, iron, calcium, copper, lead, mercury, tiary aromatic amines, e. g., quinoline and manganese, magnesium, and tin. Other salts pyridine. may be prepared, such as the salts oi. ammonia Other derivatives such as the organic esters of and substituted ammonias, for example, primary these new monoor bis-dithiocarbamic acids of aliphatic amines, e. g., methylamine, ethylamine, this invention, may be readily prepared, for examylamlne, dodecylamine; secondary aliphatic ample, by treating a salt of the monoor bisamines, e. g., dimethylamlne, diamylamine, ethyl dithiocarbamic acid with an organic halide in propylamine; primary aromatic amines, e. 3., an inert organic solvent, separating by filtrabeta-naphthylamine and p-methylaniline; section the halide salt which precipitates and isolatondary aromatic amines, e. g., diphenylamine, ing the organic ester of the monoor bis-dithio- N-ethylaniline, N-butylaniline; primary aromatcarbamic acid from the reaction solvent. Among ic-aliphatic amines, e. g., z-phenylethylamine, 3- the organic halides that can be used in making phenylpropylamine; secondary aromatic -alithese derivatives, there may be mentioned: al-

phatic amines, e. g., di-Z-phenylethylamine and kenyl halides, such as alkyl bromide; alkenyl ethyI-Z-phenylethylamine; substituted primary polyhalides such as 1,4-dichloro-2-butene; alkyl aliphatic amines, e. g., 2-ch1oroethylamine, 3- halides such as ethyl iodide; alkyl polyhalides n t p py e, 4-ethoxybuty1amine. l-phensuch as methylene chloride; aromatic halides such oxy-fim a e; Substituted Secondary alias 1,3-dinitro-5-chlorobenzene; aralkyl halides phallic amines, O 'O Y y such as 2-pheny1ethylchloride. The preparation amine, N-methyl-3-nitropropylamine, y of such organic ester derivatives may be de- 2-phenoxyethylamine; substituted primary aroscribed by the following equation utilizing dimatic amines, e. g., 4-nitroaniline, 3-ch1orosodium 4,4 -methylenebis(cyclohexanedithioaniline, 2-ethylaniline, 4-ethoxy-2-chloroaniline, carbamate) and benzyl chloride for purposes of 4-aminodiphenyl ether; substituted secondary illustration:

CHr-CH: CHr-CH! s s Nast mnc onomo oarm sm @cmm GE -C CHPC I CH3-CH3 CHI-CHI S CHa-G l CH:C

aromatic amines, e. g., N-methyl-p-chloroaniline, Many other salts or esters will be readily apparent N-phenyl-p-nitroaniline; substituted primary to those skilled in the art.

aliphatic-aromatic amines, e. g., 2-(4-chloro- The dialicyclic thiuram disulfides of this invenphenyl) ethylamine, 3 (3 nitrophenyl) propyltion are readily prepared by oxidizing the dialiamine; substituted secondary aliphatic-aromatic cyclic dithiocarbamic acids or salts of this invenamines, e. g., N-methyl-2- (4-chlorophenyl) ethyltion with oxidizing agents such as iodine, bromine,

amine, N-ethy1-3-(4-ethoxyphenyl) propylamine; chlorine, sodium nitrite, peroxides or any other primary cycloaliphatic amines, e. g., cyclohexyloxidizing agent disclosed in the literature as efamine and 2-aminodecahydronaphthalene; secfective in such capacity. Such oxidizing agents ondary cycloaliphatic amines, e. g., dicyclohexylmay be added directly to the reaction mixture amine and N- -methylcyclohexylamine; substiused for the preparation of the dithiocarbamic tuted primary cy'cloaliphatic amines, e. g., 4- acids in which case, of course, the thiuram disulnitrocyclohexylamine, 3-chlorocyclohexylamine; fide is obtained directly.

s GHQ-0H, GET-CH1 s ms-Ji-rrno CH-CHz-C oHNHJ J-sm 01,

CHr-C 1 CH:C 2

, CHr-CHg CHPCH: S S I c CH-CHz-C CHNH S-Sg-NH- L \CHPCQ1 CHPC 2 J:

substituted secondary cycloaliphatic amines, e. g., These dialicyclic thiuram disulfides may be N-methyl- 4-chlorocyclohexylamine, N-ethy1-4- converted to the corresponding thiuram monoethoxycyclohexylamine; polyamines, e. g., ethyl- I sulfides by reaction with potassium cyanide, e. g. enediamine, hexamethylenediamine, N,N'-diethaccording to the following equation The dialicyclic thiuram monosulfides may also be prepared by treating a salt of the dialicyclic monoor bis-dithiocarbamic acid with phosgene and subsequently pyrolyzing the resulting product at relatively low temperatures thus splitting out carbon oxysulfide and forming the desired prod- The thiuram monoand di-sulfides prepared as described above from the dialicyclic bis-dithiocarbamates of this invention may be polymeric.

These various salts, esters and sulfides of the monoor bis-dithiocarbamic acids of dialicyclic diamines are useful as accelerators for the vulcanization of rubber. Preferred are the salts due to their superior accelerator action and also their stability in aqueous solution or suspension. The salts of divalent metallic elements can be used as bactericides and fungicides.

Other derivatives such as, for example, isothiocyanates may be readily prepared from the dithiocarbamic acids and their salts of this invention. For instance, methylenedi-1,4-cyclohexylene diisothiocyanate may be prepared as described in the following paragraphs:

A suspension of disodium 4,4'-methylenebis- (cyclohexanedithiccarbamate) was prepared in the following manner in which the parts given are by weight:

A solution of 284 parts of bis(4-aminocyclohexyl)methane in 110 parts of 1,4-dioxane was added dropwise with stirring to a cooled to C.) mixture of 108 parts of sodium hydroxide, 208 parts of carbon disulfide and 800 parts of water in a reactor fitted with a reflux water condenser. The reaction mixture was allowed to warm to 45 C. during the addition and when the reaction was completed was heated on the steam bath for minutes in such a fashion as to avoid foaming. This suspension of disodium 4,4- methylenebis(cyclohexanedithiocarbamate) was then cooled to C. and 320 parts of ethyl chlorocarbonate added dropwise with stirring. After the addition was complete, the mixture was heated for.30 minutes on the steam bath with stirring. After cooling to room temperature, the separated oily solid was extracted from the reaction mixture with di'ethyl ether. The ether extract was washed with dilute sodium hydroxide,

dilute hydrochloric acid and finally with water;

dried over calcium chloride and the'ether removed by distillation leaving 374 parts of yellow oil. This was made to crystallize by stirring in 200 parts of methanol at room temperature. The solid was separated by filtration and subsequently Sisal KSCN .ix

recrystallized from a mixture of 240 parts of n- 10 butanol and 200 part of methanol. There was H, 7.5%; N, 9.5%; S, 21.8%. Found: C, 61.0%; H, 7.7%; N, 9.3%; S, 21.7%.

These alicyclic monoand diisothiocyanates, respectively, may be reacted with primary or secondary monoalcohols to give dialicyclic monoand diurethanes and with primary or secondary glycols to give diand polyurethanes.

The foregoing detailed description has been given for clearness of understanding only and no unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described for obvious modifications will occur to those skilled in the art.

What is claimed is:

1. A member of the class consisting of dithiocarbamic acids. their salts, and their esters, said acid having the formula CH2CH7 S (IE-Na s?! CHz-C z ANHC wherein A is a radical of the class consisting of hydrogen and C H2- 0 Hz C HNHCSSH C Hz-C 2 HSSCNHCH where m is a cardinal number not greater than 4. 3. A salt of a dithiocarbamic acid of the formula CHr-CHz CHz-CH:

HSSCNHC CH(CHz).-CH CH-NHCBSH CHr-C 2 CHz-C 2 wherein m is a cardinal number not greater than 4.

4. A salt of a metal, of valence not greater than 2, of a dithiocarbamic acid of the formula CHz-CHg CHTCH: HSSCNHCQ CH-(CHzh-C CH-NHCSSH CHz-C z c z-C 2 wherein m is a cardinal number not greater than 4.

5. 4,4 m e t h y 1 e n e b is(cyclohexanedlthiobamic acid).

6. A salt of 4,4'-methylenebis(cyclohexanedlthiocarba-mic acid) 7. A salt of a metal, of valence not greater than 2, of 4,4 methylenebis(cyclohexanedlthiocarbamlc acid) WILLIAM KIRK, JR.

REFERENCES CITED The following references are of record in the file of this patent:

Number Number UNITED STATES PATENTS Name Date Hunt et al. Nov. 10, 1936 Matheson Dec. 9, 1941 Dean Feb. 1, 1944 FOREIGN PATENTS Country Date Great Britain of 1933 

1. A MEMBER OF THE CLASS CONSISTING OF DITHIOCARBAMIC ACIDS, THEIR SALTS, AND THEIR ESTERS, SAID ACID HAVING THE FORMULA 